CN113179643B - Catalyst component for olefin polymerization - Google Patents
Catalyst component for olefin polymerization Download PDFInfo
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- CN113179643B CN113179643B CN201980081155.3A CN201980081155A CN113179643B CN 113179643 B CN113179643 B CN 113179643B CN 201980081155 A CN201980081155 A CN 201980081155A CN 113179643 B CN113179643 B CN 113179643B
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- catalyst component
- solid catalyst
- porosity
- component according
- compound
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 6
- 239000011949 solid catalyst Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 15
- 229910052753 mercury Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000002459 porosimetry Methods 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- -1 polypropylene Polymers 0.000 description 15
- 239000002245 particle Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SJLZBOWUXRTJHY-UHFFFAOYSA-N C(CC)C(CC(=O)OCC)(CC(=O)OCC)CCC Chemical compound C(CC)C(CC(=O)OCC)(CC(=O)OCC)CCC SJLZBOWUXRTJHY-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- GLADVNXLFJLYNQ-UHFFFAOYSA-N diethyl 3-tert-butyl-3-methylpentanedioate Chemical compound CCOC(=O)CC(C)(C(C)(C)C)CC(=O)OCC GLADVNXLFJLYNQ-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- MHBKFCKENPGDQF-UHFFFAOYSA-N 1-cyclohexyl-2-ethoxyethanone Chemical compound CCOCC(=O)C1CCCCC1 MHBKFCKENPGDQF-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- PBBVQPMWCFJZJC-UHFFFAOYSA-N 2-ethoxy-1-[9-(2-ethoxyacetyl)fluoren-9-yl]ethanone Chemical compound C1=CC=C2C(C(=O)COCC)(C(=O)COCC)C3=CC=CC=C3C2=C1 PBBVQPMWCFJZJC-UHFFFAOYSA-N 0.000 description 1
- 101100112111 Caenorhabditis elegans cand-1 gene Proteins 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VKLUSDSQTRAAFL-UHFFFAOYSA-N bis(2-methylpropyl) 3-(2-methylpropyl)pentanedioate Chemical compound CC(C)COC(=O)CC(CC(C)C)CC(=O)OCC(C)C VKLUSDSQTRAAFL-UHFFFAOYSA-N 0.000 description 1
- SWOQHXMPKYETNY-UHFFFAOYSA-N bis(2-methylpropyl) 3-ethylpentanedioate Chemical compound CC(C)COC(=O)CC(CC)CC(=O)OCC(C)C SWOQHXMPKYETNY-UHFFFAOYSA-N 0.000 description 1
- LLCWNYZFFVWWLX-UHFFFAOYSA-N bis(2-methylpropyl) 3-methyl-3-(2-methylpropyl)pentanedioate Chemical compound CC(C)COC(=O)CC(C)(CC(C)C)CC(=O)OCC(C)C LLCWNYZFFVWWLX-UHFFFAOYSA-N 0.000 description 1
- SZKROOFLACXITG-UHFFFAOYSA-N bis(2-methylpropyl) 3-methylpentanedioate Chemical compound CC(C)COC(=O)CC(C)CC(=O)OCC(C)C SZKROOFLACXITG-UHFFFAOYSA-N 0.000 description 1
- HYLPEFVHIQLPGJ-UHFFFAOYSA-N bis(2-methylpropyl) 3-phenylpentanedioate Chemical compound CC(C)COC(=O)CC(CC(=O)OCC(C)C)C1=CC=CC=C1 HYLPEFVHIQLPGJ-UHFFFAOYSA-N 0.000 description 1
- RARMGMGGCVSHER-UHFFFAOYSA-N bis(2-methylpropyl) 3-propan-2-ylpentanedioate Chemical compound CC(C)COC(=O)CC(C(C)C)CC(=O)OCC(C)C RARMGMGGCVSHER-UHFFFAOYSA-N 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- GPTXWRGISTZRIO-UHFFFAOYSA-N chlorquinaldol Chemical compound ClC1=CC(Cl)=C(O)C2=NC(C)=CC=C21 GPTXWRGISTZRIO-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- WKLBAFKOKJVNMN-UHFFFAOYSA-N diethyl 3,3-dimethylpentanedioate Chemical compound CCOC(=O)CC(C)(C)CC(=O)OCC WKLBAFKOKJVNMN-UHFFFAOYSA-N 0.000 description 1
- VIYRHXNXDQLXFH-UHFFFAOYSA-N diethyl 3-(2-methylpropyl)pentanedioate Chemical compound CCOC(=O)CC(CC(C)C)CC(=O)OCC VIYRHXNXDQLXFH-UHFFFAOYSA-N 0.000 description 1
- STPALKIJJSAYDG-UHFFFAOYSA-N diethyl 3-(cyclohexylmethyl)pentanedioate Chemical compound CCOC(=O)CC(CC(=O)OCC)CC1CCCCC1 STPALKIJJSAYDG-UHFFFAOYSA-N 0.000 description 1
- PMEULZQDXVXNLR-UHFFFAOYSA-N diethyl 3-butyl-3-methylpentanedioate Chemical compound CCOC(=O)CC(C)(CCCC)CC(=O)OCC PMEULZQDXVXNLR-UHFFFAOYSA-N 0.000 description 1
- JFAITBVHKGGFLX-UHFFFAOYSA-N diethyl 3-butyl-3-phenylpentanedioate Chemical compound CCOC(=O)CC(CCCC)(CC(=O)OCC)C1=CC=CC=C1 JFAITBVHKGGFLX-UHFFFAOYSA-N 0.000 description 1
- FLDRVUFUVFCBEU-UHFFFAOYSA-N diethyl 3-ethyl-3-methylpentanedioate Chemical compound CCOC(=O)CC(C)(CC)CC(=O)OCC FLDRVUFUVFCBEU-UHFFFAOYSA-N 0.000 description 1
- UFGHTNILKVQENH-UHFFFAOYSA-N diethyl 3-ethylpentanedioate Chemical compound CCOC(=O)CC(CC)CC(=O)OCC UFGHTNILKVQENH-UHFFFAOYSA-N 0.000 description 1
- HWRXSDZZXQITJD-UHFFFAOYSA-N diethyl 3-methyl-3-(2-methylpropyl)pentanedioate Chemical compound CCOC(=O)CC(C)(CC(C)C)CC(=O)OCC HWRXSDZZXQITJD-UHFFFAOYSA-N 0.000 description 1
- ZXIKKZKLTUPPFQ-UHFFFAOYSA-N diethyl 3-methyl-3-propan-2-ylpentanedioate Chemical compound CCOC(=O)CC(C)(C(C)C)CC(=O)OCC ZXIKKZKLTUPPFQ-UHFFFAOYSA-N 0.000 description 1
- GSDRMAHJAKQAOZ-UHFFFAOYSA-N diethyl 3-phenylpentanedioate Chemical compound CCOC(=O)CC(CC(=O)OCC)C1=CC=CC=C1 GSDRMAHJAKQAOZ-UHFFFAOYSA-N 0.000 description 1
- VXHFAMSEJYNPMD-UHFFFAOYSA-N diethyl 3-propan-2-ylpentanedioate Chemical compound CCOC(=O)CC(C(C)C)CC(=O)OCC VXHFAMSEJYNPMD-UHFFFAOYSA-N 0.000 description 1
- WASGQQQMQHZYNB-UHFFFAOYSA-N diethyl 3-propylpentanedioate Chemical compound CCOC(=O)CC(CCC)CC(=O)OCC WASGQQQMQHZYNB-UHFFFAOYSA-N 0.000 description 1
- ANBMJAKRRFOULQ-UHFFFAOYSA-N diethyl 3-tert-butylpentanedioate Chemical compound CCOC(=O)CC(C(C)(C)C)CC(=O)OCC ANBMJAKRRFOULQ-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012721 stereospecific polymerization Methods 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JAYPHJBLPAEMEX-UHFFFAOYSA-N trimethoxy(2-methylpentan-2-yl)silane Chemical compound CCCC(C)(C)[Si](OC)(OC)OC JAYPHJBLPAEMEX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/651—Pretreating with non-metals or metal-free compounds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/657—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in groups C08F4/653 - C08F4/656
- C08F4/6574—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in groups C08F4/653 - C08F4/656 and magnesium or compounds thereof
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
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Abstract
A solid catalyst component for the polymerization of olefins comprising Mg, ti, halogen and an electron donor compound selected from glutarates, said catalyst being characterized by specific porosity characteristics and being capable of producing olefin polymers having a low bulk density and a relatively high porosity.
Description
Technical Field
The present disclosure relates to the field of chemistry. In particular, the present invention relates to catalyst components for the polymerization of olefins, characterized by specific chemical and physical properties. The disclosed catalysts are particularly useful for preparing porous propylene polymers.
Background
The most important class of propylene polymers consists of so-called heterophasic copolymer compositions made of a relatively high crystallinity propylene polymer fraction and a low crystallinity elastomeric component (e.g. propylene-ethylene copolymer).
While these compositions may be prepared by mechanical blending of the two major components, they are more typically prepared via sequential polymerization techniques wherein a relatively high crystalline propylene polymer (sometimes referred to as a crystalline matrix) is prepared in a first polymerization reactor and then transferred to a continuous polymerization reactor where a low crystallinity elastomeric component is formed.
In this type of process, the porosity of the relatively high crystallinity polymer matrix can affect the incorporation of the elastomeric portion into the crystalline matrix.
In fact, as a general rule, the higher the porosity of the polymer matrix prepared in the first step, the higher the amount of elastomer component that can be incorporated in said matrix in the second polymerization step.
On the other hand, if the matrix has a poor porosity, the presence of excess elastomeric polymer portions on the surface of the particles increases the tackiness of said particles considerably, which causes aggregation phenomena that may cause the reactor to be on the underside, such as reactor wall sheeting, plugging or even clogging.
Macroscopic measurements of polymer porosity are given by polymer bulk density. Bulk density or apparent density is the mass per unit volume of a material, including voids inherent in the material of interest. In the case of polymer particles having a regular morphology, a relatively low bulk density value indicates a relatively high porosity of the polymer powder. Thus, for at least some applications, it is desirable to produce propylene polymers having both higher porosity (lower bulk density) and high crystallinity in the first polymerization step.
One option for producing crystalline polymers having a certain level of porosity is to polymerize propylene with a catalyst already having a certain level of porosity.
Such catalysts can be obtained starting from adducts of formula MgCl 2·mEtOH·nH2 O, where m is between 1 and 6 and n is between 0.01 and 0.6, from which a certain amount of alcohol is removed, thus yielding a porous precursor, which is then converted into the catalyst component by reaction with a titanium compound containing at least one Ti-Cl bond, as disclosed in EP 395083.
As a disadvantage, an increase in the catalyst porosity can lead to a corresponding decrease in the catalyst performance in terms of polymerization activity.
In WO2004/026920, it is proposed to prepare adducts with increased amounts of alcohols and featuring specific X-ray diffraction spectra. These adducts, once converted to catalyst components containing phthalates as internal donors, are able to produce catalysts with increased activity or, if the adducts are partially dealcoholated before reacting with Ti compounds, have a higher porosity with respect to those produced from adducts with the same amount of alcohol directly obtained in the preparation and not dealcoholated. Nevertheless, there remains a need for catalysts capable of producing crystalline polypropylene with still increased porosity.
The applicant has now found a catalyst component capable of producing propylene polymers having simultaneously low bulk density, high porosity and high crystallinity.
Disclosure of Invention
Thus, the present disclosure relates to a solid catalyst component for the polymerization of olefins comprising Mg, ti, halogen and an electron donor compound selected from glutarates, said catalyst being characterized by a total porosity (determined by mercury intrusion) of at least 0.20cm 3/g, obtained from pores with a radius of at most 1000nm, provided that more than 50% of said porosity is obtained from pores with a radius of 1 to 100 nm.
Detailed Description
In a preferred embodiment of the present disclosure, the total mercury porosity of the adduct is from 0.25 to 0.80cm 3/g, preferably from 0.35 to 0.60cm 3/g.
The fraction of porosity resulting from pores having a radius of 1 to 100nm is preferably at least 50% to 90% of the total porosity, preferably 55.0 to 85% of the total porosity, more preferably 60 to 80% of the total porosity.
Preferred glutarates are those of formula (I):
Wherein the groups R 1 to R 8 are identical or different from each other and are H or C 1-C20 straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups optionally containing heteroatoms, and two or more of said groups may also be joined to form a ring, with the proviso that neither R 7 nor R 8 is hydrogen.
One class of interesting substituted glutarates is that wherein R 1 is H and R 2 is selected from the group consisting of linear or branched C 1-C10 alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl. Preferably, R 2 is selected from the group consisting of linear or branched C 1-C10 alkyl, cycloalkyl and arylalkyl.
In a preferred embodiment, in the compound of formula (I), R 1 and R 2 are both different from hydrogen and are selected from the group consisting of linear or branched C 1-C10 alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl. Preferably, R 1 and R 2 are both selected from C 2-C5 linear alkyl groups.
R 7 and R 8 are preferably primary alkyl, arylalkyl or alkylaryl groups having from 1 to 10 carbon atoms. More preferably they are primary branched alkyl groups having from 1 to 8 carbon atoms. Examples of suitable R 7 and R 8 groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.
Specific examples of B-monosubstituted glutarate compounds are diisobutyl 3-methylglutarate, diisobutyl 3-phenylglutarate, diethyl 3-ethylglutarate, diethyl 3-n-propylglutarate, diethyl 3-isopropylglutarate, diethyl 3-isobutylglutarate, diethyl 3-phenylglutarate, diisobutyl 3-ethylglutarate, diisobutyl 3-isopropylglutarate, diisobutyl 3-isobutylglutarate, diethyl 3- (3, 3-trifluoropropyl) glutarate, diethyl 3-cyclohexylmethylglutarate, diethyl 3-t-butylglutarate.
Specific examples of di-or tri-substituted glutarates are: 3, 3-Dimethylglutarate diethyl ester, 3-Dimethylglutarate diisobutyl ester, 3-methyl-3-isobutylglutarate diethyl ester, 3-methyl-3-tert-butylglutarate diethyl ester, 3-methyl-3-isobutylglutarate diisobutyl ester, 3-methyl-3-phenylglutarate diethyl ester 3, 3-Di-n-propylglutarate diethyl ester, 3-di-n-propylglutarate diisobutyl ester, 3-diisobutylglutarate diethyl ester, 3-methyl-3-butylglutarate diethyl ester, 3-diphenylglutarate diethyl ester, 3-methyl-3-ethylglutarate diethyl ester, 3-diethylglutarate diethyl ester 3-methyl-3-isopropyl-glutarate diethyl ester, 3-phenyl-3-n-butyl-glutarate diethyl ester, 3-methyl-3-tert-butyl-glutarate diethyl ester, 3-diisopropyl-glutarate diisobutyl 3-methyl-3-phenyl-glutarate diisobutyl 3, 3-diisobutyl-glutarate diisobutyl 3-methyl-3-butyl-glutarate diisobutyl 3, 3-diphenyl-glutarate diisobutyl 3-methyl-3-ethyl-glutarate diisobutyl 3, 3-diethyl-glutarate diisobutyl 3-methyl-3-isopropyl-glutarate diisobutyl 3-phenyl-3-n-butyl-glutarate diisobutyl, 3-methyl-3-tert-butylglutarate diisobutyl, 3-diisopropylglutarate diisobutyl, 3-ethyl-3-n-butylglutarate diethyl, 3-ethyl-3-n-butylglutarate diisobutyl, 3-isopropyl-3-n-butylglutarate diethyl, 3-isopropyl-3-n-butylglutarate diisobutyl, 3- (2-methyl-butyl) -3-ethylglutarate diisobutyl, 3-n-propyl-3-phenylglutarate diethyl, 2-methyl-3-phenylglutarate diethyl, 2-dimethyl-3-phenylglutarate diethyl, 2-methyl-3, 3-diisobutylglutarate diethyl, 2-ethyl-3-isopropylglutarate diisobutyl, 2-methyl-3-phenylglutarate diisobutyl, 2, 4-dimethyl-3-diisobutyl glutarate diisobutyl, 2-diisobutyl glutarate diisobutyl. Among them, diethyl 3, 3-di-n-propylglutarate and diisobutyl 3, 3-di-n-propylglutarate are most preferable.
Specific examples of glutarates in which substituents R 1 and R 2 are linked to form a ring are 9, 9-bis (ethoxyacetyl) fluorene, 1-bis (ethoxyacetyl) cyclopentane, 1-bis (ethoxyacetyl) cyclohexane, 1, 3-bis (ethoxycarbonyl) -1, 2-trimethylcyclopentane.
The catalyst component of the precursor of the present disclosure having the above-described characteristics can be obtained according to several methods. According to a preferred one, an adduct between magnesium chloride and an alcohol (in particular ethanol) containing 3.5 to 4.5 moles of alcohol per mole of Mg is prepared.
The adducts may be prepared by contacting MgCl 2 with an alcohol in the absence of an inert liquid dispersant, heating the system at or above the melting temperature of MgCl 2 -alcohol adduct, and maintaining the conditions to obtain a fully molten adduct. In particular, the adduct is preferably maintained under stirring conditions at a temperature equal to or higher than its melting temperature for a period of time equal to or greater than 1 hour, preferably from 2 to 15 hours, more preferably from 5 to 10 hours. The molten adduct is then emulsified in a liquid medium which is immiscible with and chemically inert to it and finally quenched by contacting the adduct with an inert cooling liquid, thereby obtaining solidification of the adduct. It is also preferred that the solid particles are left in the cooling liquid at a temperature of-10 to 25 ℃ for a time of 1 to 24 hours before they are recovered. In particular, in this process, the solidification of the adducts in spherical particles can be obtained by spraying the non-emulsified MgCl 2 -alcohol adducts in an environment having a temperature as low as to cause rapid solidification of the particles.
In a variant of this process, particles of MgCl 2 may be dispersed in an inert liquid that is immiscible with and chemically inert to the molten adduct, the system heated at a temperature equal to or higher than the melting temperature of the MgCl 2 -ethanol adduct, and then the desired amount of alcohol added in the gas phase. The temperature is maintained at a value such that the adduct is completely melted for a period of time ranging from 10 minutes to 10 hours. The molten adduct is then treated as described above. The liquid in which MgCl 2 or emulsified adducts are dispersed may be any liquid that is not miscible with and chemically inert to the molten adducts. For example, aliphatic, aromatic or alicyclic hydrocarbons and silicone oils may be used. Aliphatic hydrocarbons such as vaseline oil are particularly preferred.
The quench liquid is preferably selected from hydrocarbons that are liquid at temperatures in the range of-30 to 30 ℃. Among them, pentane, hexane, heptane or a mixture thereof is preferred.
In another variant, the molten adduct obtained is solidified into discrete particles by using spray cooling techniques, wherein the solidification takes place immediately by spraying the solution through a nozzle in a cold environment.
The solid adducts thus obtained are made from dense particles with low mercury porosity, which may be in the range of 0.05 to 0.12cm 3/g.
Mercury porosity may be increased by a dealcoholation step carried out according to known methods, such as those described in EP-a-395083, wherein dealcoholation is obtained by maintaining the adduct particles in an open circulating fluidized bed created by a flow of hot nitrogen, which is directed out of the system after removal of the alcohol from the adduct particles. In this open-loop treatment, dealcoholization is carried out under an elevated temperature gradient until the particles have reached the desired alcohol content, which in any case is at least 10% lower than the initial amount.
The partially dealcoholated adducts thus obtained may exhibit a porosity of-0.15 to 1.5cm 3/g, depending on the degree of alcohol removed.
The particles collected at the end of the treatment form are then reacted with a titanium compound and glutarate to form the final solid catalyst component. Particularly preferred titanium compounds are those of the formula Ti (OR a)nXy-n, where n is comprised between 0 and y; y is the valence of titanium; X is chlorine and R a is a hydrocarbon radical, preferably an alkyl radical, having from 1 to 10 carbon atoms OR a group COR a. Among these, titanium compounds having at least one Ti-Cl bond are particularly preferred, for example titanium tetrachloride OR chlorohydrinates. Preferred specific titanium compounds are TiCl3、TiCl4、Ti(OBu)4、Ti(OBu)Cl3、Ti(OBu)2Cl2、Ti(OBu)3Cl. are preferably reacted by suspending the adduct in cold TiCl 4 (usually 0 ℃ OR less; the mixture thus obtained is then heated to 80-130 ℃ and held at this temperature for 0.5-2 hours. After removal of excess TiCl 4 and recovery of the solid component. Treatment with TiCl 4 may be carried out one OR more times.
The solid catalyst component described in the present application may contain Ti atoms in an amount of more than 0.5wt%, more preferably more than 1.0wt%, particularly more than 1.5wt% relative to the total weight of the catalyst component. The amount of titanium is particularly preferably from 1.50 to 5% by weight, relative to the total weight of the catalyst component.
The solid catalyst component may also contain small amounts of further metal compounds selected from those containing elements belonging to groups 1-15, preferably 11-15 of the periodic table of the elements (Iupac version).
Most preferably, the compound comprises an element selected from Cu, zn and Bi without metal-carbon bonds. Preferred compounds are oxides, carbonates, alkoxides, carboxylates and halides of the metals. Among them, znO, znCl 2、CuO、CuCl2 and copper diacetate, biCl 3, bismuth carbonate and bismuth carboxylate are preferable.
The compounds may be added during the preparation of the magnesium-alcohol adducts described previously, or they may be introduced into the catalyst by dispersing them into the titanium compound in liquid form and then reacting with the adducts.
Whichever method is used, the final amount of metal into the final catalyst component is from 0.1 to 10wt%, preferably from 0.3 to 8wt% and most preferably from 0.5 to 5wt%, relative to the total weight of the solid catalyst component.
An electron donor compound (glutarate as internal donor) may be added during the reaction between titanium compound and adduct in such an amount that the ratio glutarate to Mg is from 1:4 to 1:20.
In a preferred embodiment, the electron donor compound is added during the first treatment with TiCl 4.
Regardless of the preparation method used, the final amount of glutarate in the solid catalyst component should be such that its molar ratio relative to Ti atoms is from 0.01:1 to 2:1, preferably from 0.05:1 to 1.2:1.
The glutarate donor may be added as such during the catalyst preparation or, alternatively, in the form of a precursor which is able to be converted in the compound of formula (I) as a result of reaction with other catalyst components. The solid catalyst component may contain, in addition to glutarates, further donors. Although there is no limitation on the type of additional donor that may be selected from esters, ethers, carbamates, thioesters, amides and ketones.
Among the above-mentioned classes, particular preference is given to 1, 3-diethers of the formula (II)
Wherein R I and R II are the same or different and are hydrogen or straight or branched C 1-C18 hydrocarbyl groups which may also form one or more cyclic structures; the R III groups, equal to or different from each other, are hydrogen or C 1-C18 hydrocarbyl; the R IV groups are identical to or different from each other and have the same meaning as R III, except that they cannot be hydrogen; the RI to R IV groups may each contain heteroatoms selected from halogen, N, O, S and Si.
Preferably, R IV is an alkyl group of 1 to 6 carbon atoms, more particularly methyl, and the R III group is preferably hydrogen. Further, when R I is methyl, ethyl, propyl, or isopropyl, R II may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl, or benzyl; when R I is hydrogen, R II may be ethyl, butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl, p-chlorophenyl, 1-naphthyl, 1-decalinyl; r I and R II may be the same, and may be ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, phenyl, benzyl, cyclohexyl, or cyclopentyl.
Particular preference is given to compounds of the formula (III):
Wherein the R VIVI groups are the same or different and are hydrogen; halogen, preferably Cl and F; a linear or branched Cl-C20 alkyl group; c 3-C20 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl and C 7-C20 arylalkyl, optionally containing one or more heteroatoms selected from N, O, S, P, si and halogen, in particular Cl and F, as substituents of carbon atoms or hydrogen atoms, or both; the radicals R Ⅲ and R IV are as defined above for formula (II).
Surprisingly, the catalyst components of the present disclosure are capable of producing polymers having higher porosities (lower bulk densities) despite similar levels of total porosity relative to catalyst components prepared from precursors that do not have the combination of features.
The catalyst components of the present disclosure form catalysts for the polymerization of alpha-olefins CH 2 =chr, where R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms, by reaction with an alkyl aluminum compound. The alkyl-Al compound is preferably selected from trialkylaluminum compounds, such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to optionally use alkyl aluminum halides, alkyl aluminum hydrides or alkyl aluminum sesquichlorides such as A1Et 2 Cl and Al 2Et3Cl3 in mixtures with the trialkylaluminum compounds.
The molar ratio between the alkyl-Al compound and the Ti of the solid catalyst component may be from 20:1 to 2000:1.
In the case of the stereospecific polymerization of alpha-olefins such as propylene and 1-butene, an electron donor compound (external donor), which may be the same or different from the compound used as internal donor, may be used to prepare the above-mentioned catalyst. In the case where the internal donor is an ester of a polycarboxylic acid, in particular a phthalate, the external donor is preferably selected from silicon compounds containing at least one Si-OR bond having formula R a 1Rb 2Si(OR3)c, wherein a and b are integers from 0 to 2, c is an integer from 1 to 3 and the sum of (a+b+c) is 4; r 1、R2 and R 3 are alkyl, cycloalkyl or aryl groups having 1 to 18 carbon atoms. Particularly preferred are silicon compounds wherein a is 1, b is 1, C is 2, at least one of R 1 and R 2 is selected from branched alkyl, cycloalkyl or aryl groups having 3 to 10 carbon atoms, and R 3 is a C 1-C10 alkyl group, particularly methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxy silane, diphenyldimethoxy silane, methyl tert-butyldimethoxy silane, dicyclopentyl dimethoxy silane. Furthermore, silicon compounds wherein a is 0, c is 3, R 2 is branched alkyl or cycloalkyl, and R 3 is methyl are also preferred. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and t-hexyltrimethoxysilane.
As previously described, the components of the present disclosure and catalysts obtained therefrom are useful in (co) polymerization processes of olefins of formula CH 2 =chr, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms.
The catalysts of the present disclosure may be used in any olefin polymerization process known in the art. They can be used, for example, in slurry polymerizations using inert hydrocarbon solvents as diluents or bulk polymerizations using liquid monomers (e.g., propylene) as reaction medium. In addition, they can also be used in polymerization processes operating in the gas phase in one or more fluidized-bed or mechanically stirred-bed reactors.
The polymerization may be carried out generally at a temperature of from 20 to 120℃and preferably from 40 to 80 ℃. When the polymerization is carried out in the gas phase, the operating pressure may be from 0.1 to 10MPa, preferably from 1 to 5MPa. In bulk polymerization, the operating pressure is generally from 1 to 6MPa, preferably from 1.5 to 4MPa.
The following examples are given for the purpose of illustration and not limitation of the disclosure itself.
Characterization of
Porosity and surface area of nitrogen: measured according to the b.e.t. method (device using SORPTOMATIC a 1900 of Carlo Erba).
Porosity and surface area of mercury:
Measurements were made using a "Pascal 240" series porosimeter from Carlo Erba.
The porosity is determined by intrusion of mercury under pressure. For this measurement, a calibrated dilatometer (capillary diameter 3 mm) CD3P (manufactured by Carlo Erba) connected to a mercury reservoir and a high vacuum pump was used. The weighed sample was placed in an dilatometer. The device was then placed under high vacuum (< 0.1mm Hg) and held under these conditions for 20 minutes. The dilatometer is then connected to the mercury reservoir and the mercury is allowed to slowly flow into the mercury reservoir until the mercury reaches a level at the 10em height marked on the dilatometer. The valve connecting the dilatometer to the vacuum pump was closed and then the mercury pressure was gradually increased to 140kg/cm 2 with nitrogen. Under pressure, mercury enters the pores, decreasing according to the porosity level of the material.
Porosity (cm 3/g) (for supports and catalysts obtained from pores of up to 1000nm only, and for polymers of up to 10000 nm) and pore distribution curves were directly calculated from the integral pore distribution curves as a function of the volume reduction of mercury and the applied pressure values (all of these data are provided and elaborated by a porosimeter-related computer equipped with dedicated Pascal software provided by c.erba).
The average pore diameter is determined as a weighted average by a pore distribution curve, and all values obtained by multiplying the relative volume (%) of each pore portion in the range of 0-1000nm of the curve by the average pore radius of the portion and dividing by the sum obtained by 100 are summed.
Examples
General procedure for preparation of catalyst Components
500Cm 3TiCl4 was charged into a 1 liter steel reactor equipped with a stirrer at room temperature and 0℃while stirring, and 20g of an adduct containing BiCl 3 (prepared as described in the following examples) in an amount of 60% by mole of Mg/Bi was added; at a temperature of 40 ℃, a certain amount of diethyl 3, 3-di-n-propylglutarate was introduced as internal donor so that the Mg/donor molar ratio was 14. The whole was heated to 110 ℃ over 58 minutes and these conditions were maintained over 50 minutes. After 10 minutes the stirring was stopped and the temperature was maintained at 110 ℃ to separate the liquid phase from the settled solids. The solid was further treated by adding 500cm 3 TiCl4 and an amount of diethyl 3, 3-di-n-propylglutarate as internal donor to give a Mg/donor molar ratio of 14. The mixture was heated at 110℃for 10min and maintained under stirring conditions (500 rpm) for 30 min. Stirring was then stopped and after 30 minutes the temperature was maintained at 110 ℃ to separate the liquid phase from the settled solids. 500cm 3 TiCl4 was added and the mixture was heated at 110℃for 10 minutes to further treat the solid and the conditions were maintained for 15 minutes under stirring (500 rpm). Stirring was then stopped and after 10 minutes the temperature was maintained at 110 ℃ to separate the liquid phase from the settled solids. Thereafter, washing was performed 5 times with 500cm 3 of anhydrous hexane at 90℃and 1 time with 500cm 3 of anhydrous hexane at room temperature. The solid catalyst component obtained is then dried under vacuum in a nitrogen atmosphere at a temperature of 40-45 ℃.
General procedure for propylene polymerization testing
A4 liter steel autoclave equipped with a stirrer, a pressure gauge, a thermometer, a catalyst feed system, a monomer feed line and a constant temperature jacket was used. To the reactor was added 0.01gr of the solid catalyst component, 0.76g of TEAL,0.06g of cyclohexylmethyldimethoxysilane, 3.21 propylene and 2.01 hydrogen. The system was heated to 70 ℃ over 10 minutes with stirring and held under these conditions for 120 minutes. At the end of the polymerization, the polymer is recovered by removing any unreacted monomers and dried under vacuum.
Example 1
530G of MgCl 2 and 14g of water were added with stirring at-8℃in a vessel reactor equipped with an IKA RE166 stirrer containing 963g of anhydrous EtOH. Once the addition of MgCl 2 was complete, the temperature was raised to 108 ℃ and held at this value for 20 hours. Thereafter, while maintaining the temperature at 108 ℃, the melt was fed by a volumetric pump set at 62ml/min to an emulsifying unit operating at 2800rpm together with OB55 oil fed by a volumetric pump set at 225ml/min and an emulsion of the melt into the oil was produced. While continuously feeding the melt and oil, the mixture at about 108 ℃ was continuously discharged into a vessel containing 22 liters of cold hexane, kept under agitation and cooled so that the final temperature did not exceed 12 ℃. After 24 hours, the solid particles of the recovered adduct were then washed with hexane and dried under vacuum at 40 ℃. The composition analysis showed that the particles contained 61.8wt% EtOH,1.15wt% water, the remainder being MgCl 2.
The adduct was then thermally dealcoholated in a fluidized bed under a stream of nitrogen at elevated temperature until the content of EtOH reached a chemical composition of 57.3wt%EtOH 1.2wt%H 2 O, the total porosity obtained from pores up to 1000nm being 0.18cm 3/g, the fraction of porosity obtained from pores up to 100nm accounting for 47.1% of the total porosity.
The sample of the dealcoholated adduct was then used to prepare a catalyst component characterized by containing 16wt% mg,1.8wt% ti,1.1wt% bi,10wt% glutarate, a total porosity from pores up to 1000nm of 0.273cm 3/g, a fraction of porosity from pores up to 100nm in radius accounting for 66.6% of the total porosity, according to the general procedure reported previously.
The catalyst thus obtained was then used in polymerization tests carried out according to the procedure described above. The results are reported in table 1.
Comparative example 1
The same procedure as disclosed in example 1 was used, except that diisobutyl phthalate was used instead of 3, 3-di-n-propyl glutarate in the preparation of the solid catalyst component. The latter is characterized by containing 17.5wt% Mg,1.4wt% Ti,2.7wt% Bi,8.5wt% phthalate.
The catalyst thus obtained was then used in polymerization tests carried out according to the procedure described above. The results are reported in table 1.
Example 2
The adduct prepared in example 1 containing 57.3wt% EtOH and 1.2wt% water was thermally dealcoholated in a fluidized bed in a nitrogen stream at elevated temperature until the EtOH content reached a chemical composition of 50wt% EtOH, 1.2wt% H 2 O, the total porosity resulting from pores up to 1000nm being 0.35cm 3/g and the fraction of porosity resulting from pores up to 100nm accounting for 29.1% of the total porosity.
The sample of the dealcoholated adduct was then used to prepare a catalyst component characterized by containing 16wt% mg,1.7wt% ti,1.1wt% bi,7.9wt% glutarate, a total porosity from pores up to 1000nm of 0.517cm 3/g, a fraction of porosity from pores up to 100nm in radius accounting for 60.2% of the total porosity, according to the general procedure reported previously.
The catalyst thus obtained was then used in polymerization tests carried out according to the procedure described above. The results are reported in table 1.
Comparative example 2
The initial amount of MgCl 2·2.8C2H5 OH adduct was prepared according to the method described in example 2 of PCT publication No. WO98/44009, but operated on a larger scale.
The adduct was then thermally dealcoholated under a stream of nitrogen at elevated temperature until the EtOH content reached a chemical composition of 49.8wt% EtOH and 1.3wt% water.
The sample of the dealcoholated adduct was then used to prepare a catalyst component characterized as containing 15.5wt% mg,1.5wt% ti,0.9wt% bi,9.1wt% glutarate, 0.545cm 3/g of total porosity from pores up to 1000nm, the fraction of porosity from pores up to 100nm radius accounting for 46.6% of the total porosity, according to the general procedure reported previously.
The catalyst thus obtained was then used in polymerization tests carried out according to the procedure described above. The results are reported in table 1.
TABLE 1
Claims (14)
1. A solid catalyst component for the polymerization of olefins comprising Mg, ti, halogen and an electron donor compound selected from glutarates, the catalyst being characterized by a total porosity, measured by mercury porosimetry, of 0.273 to 0.517 cm 3/g obtained from pores with a radius of up to 1000 nm, provided that more than 50% of the porosity is obtained from pores with a radius of 1 to 100 nm, wherein the amount of Ti atoms is higher than 1.5% by weight to 5% by weight relative to the total weight of the catalyst component, and wherein the solid catalyst component is obtained by subjecting an adduct between magnesium chloride containing 3.5 to 4.5 moles of alcohol per mole of Mg and an alcohol to dealcoholization conditions until a partially dealcoholized adduct is obtained, said partially dealcoholized adduct exhibiting a porosity of 0.15 to 1.5cm 3/g, and further reacting the partially dealcoholized adduct with a Ti compound in the presence of a glutarate electron donor.
2. The solid catalyst component according to claim 1 in which the fraction of porosity obtained from pores having a radius of 1 to 100 nm is at least 50% to 90% of the total porosity.
3. The solid catalyst component according to claim 2 in which the fraction of porosity obtained from pores having a radius of 1 to 100nm is 55% to 85% of the total porosity.
4. The solid catalyst component according to claim 1 in which the electron donor is selected from glutarates of formula (I)
Wherein the groups R 1 to R 8 are identical or different from each other and are H or C 1-C20 straight-chain or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups optionally containing heteroatoms, and two or more of said groups may also be joined to form a ring, with the proviso that neither R 7 nor R 8 is hydrogen.
5. The solid catalyst component according to claim 4 in which R 1 is H and R 2 is selected from the group consisting of linear or branched C 1-C10 alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl.
6. The solid catalyst component according to claim 4 in which R 1 and R 2 are both different from hydrogen and are selected from linear or branched C 1-C10 alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl.
7. The solid catalyst component according to claim 6 in which R 1 and R 2 are both selected from C 2-C5 linear alkyl groups.
8. The solid catalyst component according to claim 4 in which R 7 and R 8 are primary alkyl, arylalkyl or alkylaryl groups having from 1 to 10 carbon atoms.
9. The solid catalyst component according to claim 1 in which the Ti atom belongs to a titanium compound of formula Ti (OR a)nXy-n in which n is comprised between 0 and y, y is the valence of titanium, X is chlorine and R a is a hydrocarbon group.
10. The solid catalyst component according to claim 1, further comprising a compound of a metal selected from Cu, zn and Bi, said compound being free of metal-carbon bonds.
11. The solid catalyst component according to claim 1 further comprising an additional donor selected from esters, ethers, carbamates, thioesters, amides and ketones.
12. A catalyst for olefin polymerization comprising the reaction product between the catalyst component according to any one of claims 1 to 11 and an organoaluminum compound.
13. The catalyst for olefin polymerization according to claim 12, further comprising an external donor.
14. A process for polymerizing an olefin of the formula CH 2 =chr, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms, carried out in the presence of the catalyst according to any one of claims 12-13.
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| EP19151034.6 | 2019-01-09 | ||
| EP19151034 | 2019-01-09 | ||
| PCT/EP2019/086195 WO2020144035A1 (en) | 2019-01-09 | 2019-12-19 | Catalyst components for the polymerization of olefins |
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| US (1) | US20220081497A1 (en) |
| EP (1) | EP3908614A1 (en) |
| JP (1) | JP7106241B2 (en) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306544A (en) * | 1999-03-15 | 2001-08-01 | 巴塞尔技术有限公司 | Components and catlayst for polymierization of olefins |
| CN105263976A (en) * | 2013-01-18 | 2016-01-20 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for the polymerization of olefins |
| CN106170500A (en) * | 2014-03-14 | 2016-11-30 | 巴塞尔聚烯烃意大利有限公司 | Catalytic component for olefinic polymerization |
| CN107949587A (en) * | 2015-09-11 | 2018-04-20 | 巴塞尔聚烯烃意大利有限公司 | It is used to prepare the technique of catalyst component for olefin |
| CN107949588A (en) * | 2015-09-10 | 2018-04-20 | 巴塞尔聚烯烃意大利有限公司 | Catalyst for olefin polymerization |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1098272B (en) * | 1978-08-22 | 1985-09-07 | Montedison Spa | COMPONENTS, CATALYSTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
| IT1230133B (en) * | 1989-04-28 | 1991-10-14 | Himont Inc | PLASTIC-ELASTIC POLYPROPYLENE COMPOSITIONS |
| IT1230134B (en) | 1989-04-28 | 1991-10-14 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| JP3205439B2 (en) | 1993-08-04 | 2001-09-04 | 日立建機株式会社 | Driver's cab of work machine |
| JP4531137B2 (en) | 1997-03-29 | 2010-08-25 | バセル テクノロジー カンパニー ビー．ブイ． | Magnesium chloride-alcohol adduct, its production process and catalyst components obtained therefrom |
| US6605562B1 (en) * | 1998-11-04 | 2003-08-12 | Basell Poliolefine Italia S.P.A. | Components and catalysts for the polymerization of olefins |
| TWI268939B (en) * | 2001-12-12 | 2006-12-21 | Basell Poliolefine Spa | Process for the polymerization of olefins |
| ES2643193T3 (en) | 2002-09-17 | 2017-11-21 | Basell Poliolefine Italia S.R.L. | Adducts of magnesium-ethanol dichloride and catalyst components obtained from them |
| EP1518866A1 (en) * | 2003-09-29 | 2005-03-30 | Basell Poliolefine Italia S.P.A. | Process for the preparation of porous ethylene polymers |
| KR101150124B1 (en) | 2009-03-11 | 2012-06-08 | 에어 프로덕츠 앤드 케미칼스, 인코오포레이티드 | Method for preparing metal complexes of polydentate beta-ketoiminates |
| JP5623760B2 (en) | 2009-03-17 | 2014-11-12 | 東邦チタニウム株式会社 | Solid catalyst component and catalyst for olefin polymerization, and method for producing olefin polymer using the same |
| JP6005726B2 (en) * | 2011-04-12 | 2016-10-12 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | Catalyst components for olefin polymerization |
| EP2607386A1 (en) * | 2011-12-23 | 2013-06-26 | Basell Poliolefine Italia S.r.l. | Pre-polymerized catalyst components for the polymerization of olefins |
| EP2607387A1 (en) * | 2011-12-23 | 2013-06-26 | Basell Poliolefine Italia S.r.l. | Pre-polymerized catalyst components for the polymerization of olefins |
| CN103554312B (en) * | 2013-10-18 | 2016-08-17 | 营口市向阳催化剂有限责任公司 | A kind of internal electron donor compound for preparing alpha-olefin polymerization catalyst component |
| US10208135B2 (en) * | 2014-10-03 | 2019-02-19 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins |
-
2019
- 2019-12-19 WO PCT/EP2019/086195 patent/WO2020144035A1/en unknown
- 2019-12-19 JP JP2021539076A patent/JP7106241B2/en active Active
- 2019-12-19 US US17/419,560 patent/US20220081497A1/en not_active Abandoned
- 2019-12-19 KR KR1020217024771A patent/KR102610378B1/en active IP Right Grant
- 2019-12-19 EP EP19821110.4A patent/EP3908614A1/en active Pending
- 2019-12-19 CN CN201980081155.3A patent/CN113179643B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306544A (en) * | 1999-03-15 | 2001-08-01 | 巴塞尔技术有限公司 | Components and catlayst for polymierization of olefins |
| CN105263976A (en) * | 2013-01-18 | 2016-01-20 | 巴塞尔聚烯烃意大利有限公司 | Catalyst components for the polymerization of olefins |
| CN106170500A (en) * | 2014-03-14 | 2016-11-30 | 巴塞尔聚烯烃意大利有限公司 | Catalytic component for olefinic polymerization |
| CN107949588A (en) * | 2015-09-10 | 2018-04-20 | 巴塞尔聚烯烃意大利有限公司 | Catalyst for olefin polymerization |
| CN107949587A (en) * | 2015-09-11 | 2018-04-20 | 巴塞尔聚烯烃意大利有限公司 | It is used to prepare the technique of catalyst component for olefin |
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| CN113179643A (en) | 2021-07-27 |
| BR112021011085A2 (en) | 2021-08-31 |
| KR20210112356A (en) | 2021-09-14 |
| US20220081497A1 (en) | 2022-03-17 |
| WO2020144035A1 (en) | 2020-07-16 |
| KR102610378B1 (en) | 2023-12-05 |
| JP2022516190A (en) | 2022-02-24 |
| JP7106241B2 (en) | 2022-07-26 |
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